Abstract
Clean energy and green solvents have attracted wide attention due to their non-toxic, biodegradable, and recyclable properties. Deep eutectic solvent (DES), as a green solvent, has advantages in the formation of nanocellulose. To reveal the formation mechanism during cellulose nanocrystal (CNC) preparation, different carboxylic acid DESs are compared in the optimal experimental conditions. Experimental observations show that oxalic acid (OA) DESs can fabricate CNCs with higher yield, higher crystalline index than that of citric acid series. Moreover, crystal water molecules in DESs promote the reaction activity of DESs in the CNC formation. To understand the interaction among the DES/cellulose complex, molecular dynamics simulations and quantum chemical calculations were applied to investigate the arrangement of CNCs in the atomic scale. The radial distribution function and intermolecular interactions indicate that the non-covalent intermolecular interactions between DESs and cellulose are strong, which could be further enhanced by the crystal waters in DESs. Reaction pathways during the formation of CNCs were revealed by computational simulations, which show that OA is more prone to react with cellulose in esterification and acidolysis reactions. Both computational and experimental results demonstrate that the OA DESs are more beneficial in the production of CNCs. The synergistic effects of chemical reactions and non-covalent interactions favor the formation of CNCs by DESs.
Similar content being viewed by others
Availability of data and materials
All data generated during this study are included in this submitted article.
References
Abbott AP, Boothby D, Capper G, Davies DL, Rasheed RK (2004) Deep eutectic solvents formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids. J Am Chem Soc 126(29):9142–9147. https://doi.org/10.1021/ja048266j
Ahmadi R, Hemmateenejad B, Safavi A, Shojaeifard Z, Shahsavar A, Mohajeri A, Zolghadr AR (2018) Deep eutectic-water binary solvent associations investigated by vibrational spectroscopy and chemometrics. Phys Chem Chem Phys 20(27):18463–18473. https://doi.org/10.1039/C8CP00409A
Bader RFW (1992) Atoms in molecules. A quantum theory. Reihe: International series of monographs on chemistry, Vol. 22, Clarendon Press, Oxford
Bannwarth C, Ehlert S, Grimme S (2019) GFN2-xTB—an accurate and broadly parametrized self-consistent tight-binding quantum chemical method with multipole electrostatics and density-dependent dispersion contributions. J Chem Theory Comput 15(3):1652–1671. https://doi.org/10.1021/acs.jctc.8b01176
Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic-behavior. Phys Rev A 38(6):3098–3100. https://doi.org/10.1103/PhysRevA.38.3098
Cao B, Liu S, Du D, Xue Z, Fu H, Sun H (2016) Experiment and DFT studies on radioiodine removal and storage mechanism by imidazolium-based ionic liquid. J Mol Graph Model 64:51–59. https://doi.org/10.1016/j.jmgm.2015.10.008
Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18(13):3835–3843. https://doi.org/10.1039/C6GC00687F
Cheng M, Qin Z, Chen Y, Liu J, Ren Z (2017) Facile one-step extraction and oxidative carboxylation of cellulose nanocrystals through hydrothermal reaction by using mixed inorganic acids. Cellulose 24(8):3243–3254. https://doi.org/10.1007/s10570-017-1339-1
Dauber-Osguthorpe P, Roberts VA, Osguthorpe DJ, Wolff J, Genest M, Hagler AT (1988) Structure and energetics of ligand binding to proteins: Escherichia coli dihydrofolate reductase-trimethoprim, a drug-receptor system. Proteins 4(1):31–47. https://doi.org/10.1002/prot.340040106
Du H, Liu C, Mu X, Gong W, Lv D, Hong Y, Li B (2016) Preparation and characterization of thermally stable cellulose nanocrystals via a sustainable approach of FeCl3-catalyzed formic acid hydrolysis. Cellulose 23(4):2389–2407. https://doi.org/10.1007/s10570-016-0963-5
Du H, Liu W, Zhang M, Si C, Zhang X, Li B (2019) Cellulose nanocrystals and cellulose nanofibrils based hydrogels for biomedical applications. Carbohydr Polym 209:130–144. https://doi.org/10.1016/j.carbpol.2019.01.020
Espinosa E, Molins E, Lecomte C (1998) Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities. Chem Phys Lett 285(3–4):170–173. https://doi.org/10.1016/S0009-2614(98)00036-0
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. https://doi.org/10.1007/s10570-013-0030-4
French AD (2020) Increment in evolution of cellulose crystallinity analysis. Cellulose 27(10):5445–5448. https://doi.org/10.1007/s10570-020-03172-z
Frisch MJ, Pople JA, Binkley JS (1984) Self-consistent molecular-orbital methods 25 supplementary functions for Gaussian-basis sets. J Chem Phys 80(7):3265–3269. https://doi.org/10.1063/1.447079
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR (2016) Gaussian 16, Revision A.01, Gaussian, Inc, Wallingford CT
Fu H, Wang X, Sang H, Hou Y, Chen X, Feng X (2020) Dissolution behavior of microcrystalline cellulose in DBU-based deep eutectic solvents: insights from spectroscopic investigation and quantum chemical calculations. J Mol Liq. https://doi.org/10.1016/j.molliq.2019.112140
Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys. https://doi.org/10.1063/1.3382344
Hariharan PC, Pople JA (1973) The influence of polarization functions on molecular orbital hydrogenation energies. Theor Chim Acta 28:213–222. https://doi.org/10.1007/BF00533485
Hehre WJ, Ditchfield R, Pople JA (1972) Self-consistent molecular orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular orbital studies of organic molecules. J Chem Phys 56(5):2257–2261. https://doi.org/10.1063/1.1677527
Johnson ER, Keinan S, Mori-Sanchez P, Contreras-Garcia J, Cohen AJ, Yang W (2010) Revealing noncovalent interactions. J Am Chem Soc 132(18):6498–6506. https://doi.org/10.1021/ja100936w
Kalhor P, Zheng YZ, Ashraf H, Cao B, Yu ZW (2020) Influence of hydration on the structure and interactions of ethaline deep eutectic solvent: a spectroscopic and computational study. ChemPhysChem 21(10):995–1005. https://doi.org/10.1002/cphc.202000165
Kohn W, Becke AD, Parr RG (1996) Density functional theory of electronic structure. J Phys Chem 100(31):12974–12980. https://doi.org/10.1021/jp960669l
Lee CT, Yang WT, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37(2):785–789. https://doi.org/10.1103/PhysRevB.37.785
Lim WL, Gunny AAN, Kasim FH, Gopinath SCB, Kamaludin NHI, Arbain D (2021) Cellulose nanocrystals from bleached rice straw pulp: acidic deep eutectic solvent versus sulphuric acid hydrolyses. Cellulose 28(10):6183–6199. https://doi.org/10.1007/s10570-021-03914-7
Liu Y, Wang H, Yu G, Yu Q, Li B, Mu X (2014) A novel approach for the preparation of nanocrystalline cellulose by using phosphotungstic acid. Carbohydr Polym 110:415–422. https://doi.org/10.1016/j.carbpol.2014.04.040
Liu Y, Chen W, Xia Q, Guo B, Wang Q, Liu S, Yu H (2017a) Efficient cleavage of lignin-carbohydrate complexes and ultrafast extraction of lignin oligomers from wood biomass by microwave-assisted treatment with deep eutectic solvent. Chemsuschem 10(8):1692–1700. https://doi.org/10.1002/cssc.201601795
Liu Y, Guo B, Xia Q, Meng J, Chen W, Liu S, Yu H (2017b) Efficient cleavage of strong hydrogen bonds in cotton by deep eutectic solvents and facile fabrication of cellulose nanocrystals in high yields. ACS Sustain Chem Eng 5(9):7623–7631. https://doi.org/10.1021/acssuschemeng.7b00954
Liu S, Zhang Q, Gou S, Zhang L, Wang Z (2021) Esterification of cellulose using carboxylic acid-based deep eutectic solvents to produce high-yield cellulose nanofibers. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2020.117018
Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33(5):580–592. https://doi.org/10.1002/jcc.22885
Lu T, Chen Q (2021) Interaction region indicator: a simple real space function clearly revealing both chemical bonds and weak interactions. Chem Methods 1(5):231–239. https://doi.org/10.1002/cmtd.202100007
Martínez L, Andrade R, Birgin EG, Martínez JM (2009) PACKMOL: a package for building initial configurations for molecular dynamics simulations. J Comput Chem 30(13):2157–2164. https://doi.org/10.1002/jcc.21224
Miao J, Yu Y, Jiang Z, Zhang L (2016) One-pot preparation of hydrophobic cellulose nanocrystals in an ionic liquid. Cellulose 23(2):1209–1219. https://doi.org/10.1007/s10570-016-0864-7
Mills G, Jónsson H (1994) Quantum and thermal effects in H2 dissociative adsorption: evaluation of free energy barriers in multidimensional quantum systems. Phys Rev Lett 72(7):1124–1127. https://doi.org/10.1103/PhysRevLett.72.1124
Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40(7):3941–3994. https://doi.org/10.1039/C0CS00108B
Neese F (2012) The ORCA program system. WIRES Comput Mol Sci 2(1):73–78. https://doi.org/10.1002/wcms.81
Neese F (2022) Software update: the ORCA program system—version 5.0. WIRES Comput Mol Sci. https://doi.org/10.1002/wcms.1606
Rajinipriya M, Nagalakshmaiah M, Robert M, Elkoun S (2018) Importance of agricultural and industrial waste in the field of nanocellulose and recent industrial developments of wood based nanocellulose: a review. ACS Sustain Chem Eng 6(3):2807–2828. https://doi.org/10.1021/acssuschemeng.7b03437
Selkälä T, Sirviö JA, Lorite GS, Liimatainen H (2016) Anionically stabilized cellulose nanofibrils through succinylation pretreatment in urea-lithium chloride deep eutectic solvent. Chemsuschem 9(21):3074–3083. https://doi.org/10.1002/cssc.201600903
Sirviö JA, Visanko M, Liimatainen H (2016) Acidic deep eutectic solvents as hydrolytic media for cellulose nanocrystal production. Biomacromol 17(9):3025–3032. https://doi.org/10.1021/acs.biomac.6b00910
Smirnov MA, Sokolova MP, Tolmachev DA, Vorobiov VK, Kasatkin IA, Smirnov NN, Yakimansky AV (2020) Green method for preparation of cellulose nanocrystals using deep eutectic solvent. Cellulose 27(8):4305–4317. https://doi.org/10.1007/s10570-020-03100-1
Spinella S, Maiorana A, Qian Q, Dawson NJ, Hepworth V, McCallum SA, Gross RA (2016) Concurrent cellulose hydrolysis and esterification to prepare a surface-modified cellulose nanocrystal decorated with carboxylic acid moieties. ACS Sustain Chem Eng 4(3):1538–1550. https://doi.org/10.1021/acssuschemeng.5b01489
Tognetti V, Cortona P, Adamo C (2008) A new parameter-free correlation functional based on an average atomic reduced density gradient analysis. J Chem Phys. https://doi.org/10.1063/1.2816137
Torlopov MA, Udoratina EV, Martakov IS, Sitnikov PA (2017) Cellulose nanocrystals prepared in H3PW12O40-acetic acid system. Cellulose 24(5):2153–2162. https://doi.org/10.1007/s10570-017-1256-3
Xie H, Du H, Yang X, Si C (2018) Recent strategies in preparation of cellulose nanocrystals and cellulose nanofibrils derived from raw cellulose materials. Int J Polym Sci. https://doi.org/10.1155/2018/7923068
Xu W, Grenman H, Liu J, Kronlund D, Li B, Backman P, Xu C (2017) Mild oxalic-acid-catalyzed hydrolysis as a novel approach to prepare cellulose nanocrystals. Chemnanomat 3(2):109–119. https://doi.org/10.1002/cnma.201600347
Zhao Y, Truhlar DG (2008) Density functionals with broad applicability in chemistry. Acc Chem Res 41(2):157–167. https://doi.org/10.1021/ar700111a
Zheng YZ, Zhou Y, Liang Q, Chen DF, Guo R (2016) A theoretical study on the hydrogen-bonding interactions between flavonoids and ethanol/water. J Mol Model. https://doi.org/10.1007/s00894-016-2968-2
Acknowledgments
We appreciated Xiang Wang, Linlin Zheng and Haoyang Xu for building simulation models of the manuscript.
Funding
This work is supported by China Agriculture Research System for Bast and Leaf Fiber Crops: CARS-16, and the Fundamental Research Funds for the Central Universities (2232021A-06).
Author information
Authors and Affiliations
Contributions
Xuerong Bi performed the experiment and simulation. Jin Wen was a major contributor in analyzing data. Xuerong Bi wrote this manuscript. Chongwen Yu, Jin Wen, and Jiansheng Guo reviewed and revised the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Ethics approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Bi, X., Guo, J., Wen, J. et al. Mechanistic analysis of nanocellulose formation tuned by deep eutectic solvents. Cellulose 30, 9349–9364 (2023). https://doi.org/10.1007/s10570-023-05443-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-023-05443-x